SULFUR-CONTAINING CARBENE-METAL COMPOUNDS: GENERAL ROUTE FROM CARBON DISULFIDE MANGANESE COMPLEXES; X-RAY STRUCTURE OF 1,3-DITHIOL-2-YLIDENEMANGANESE(I) DERIVATIVE

Article abstract of DOI:10.1016/S0022-328X(00)88561-7

Chiral carbene-manganese(I) complexes have been synthesized by the cycloaddition of dimethyl acetylenedicarboxylate to the coordinated CS2 ligand in Mn(η²-CS2)(CO)(L)C5H4R (L = P(OMe)3; PMe2Ph; PMe3).Irrespective of the nature of the ligand L, these 1,3-dithiol-2-ylidenemanganese(I) complexes are stable towards isomerisation into heterometallocycles and exhibit low frequency carbonyl absorption bands in the infrared consistent with a strong electron releasing effect of the carbene ligand.The structure of Mn(CS2C2(CO2Me)2)(CO)(P(OMe)3)(C5H5) has been determined by X-ray analysis of a suitable crystal.The molecule shows a carbene carbon-manganese bond C(7)-Mn of length 1.876 Angstroem and a planar carbene which does not adopt the 1,3-dithiolium aromatic-ring geometry but contains a carbon-carbon double bond, C(8)-C(9), of length of 1.341 Angstroem.The CO2Me groups are out of the plane of the carbene ligand and two positions with equal occupancy are found for each oxygen atom O(3) and O(5) belonging to the C=O groups.